CN102784641A - Preparation method of catalyst with high-activity palladium platinum core-shell structure - Google Patents
Preparation method of catalyst with high-activity palladium platinum core-shell structure Download PDFInfo
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Abstract
The invention provides a preparation method of a catalyst with a high-activity palladium platinum core-shell structure, belonging to the technical field of fuel cells. The preparation method comprises the following steps: surface functional groups such as carboxyl, hydroxyl and sulfydryl are introduced to a carbon nanotube surface by chemical oxidation and sulfhydrylation; palladium is loaded on the carbon nanotube surface by a chemical reduction method as a core of the core-shell type catalyst; then, in Pt-contained ionized water solution, a platinum monatomic layer is formed on the Pd surface as a shell of the core-shell type catalyst by virtue of potential difference between Pt and Pd, and weak reduction of surface functional groups such as carboxyl, hydroxyl and sulfydryl. The preparation method has the advantages of simple process and low cost. The palladium platinum core-shell structure catalyst prepared according to the preparation method can effectively reduce dosage of noble metal platinum, improve utilization rate of the catalyst, replace the existing commercial Pt/C catalyst, and can be widely used for electrical automobiles, various aircrafts and portable electronic devices such as camera and a notebook computer.
Description
Technical field
The invention belongs to the fuel cell technology field, particularly a kind of preparation method of high-activity palladium platinum catalyst with core-casing structure.
Background technology
Fuel cell is the power mechanism that a battery body and fuel tank combine.The selectivity of its fuel is very high, comprises pure hydrogen, methyl alcohol, ethanol, natural gas, uses gasoline the most widely, the fuel of the battery that can act as a fuel even now.This is that other all power resources can't be accomplished at present.And be the automobile of power with the fuel cell, generally acknowledged it is the trend of 21st century certainty.Yet the high of catalyst cost is its real one of business-like key problem that realizes of puzzlement always, and its expensive main cause comes from a large amount of uses of noble metal platinum.Because the resource-constrained of platinum costs an arm and a leg, under the situation of the non-precious metal catalyst that does not find catalytic performance and Pt to compare favourably, the utilization rate of the consumption of reduction Pt, raising Pt has become more urgent.
With the transition metal is core (for example, Cu, Ni etc.), and the platinum Base Metal is the consumption that the nucleocapsid structure eelctro-catalyst of shell can reduce metal platinum effectively, and the component through control nuclear-shell can improve activity of such catalysts.Although catalyst with core-casing structure can reduce the Pt carrying capacity, but still face following problem: how (1) further optimizes the preparation condition of catalyst with core-casing structure, seeks simple, ripe, with low cost method to improve activity of such catalysts and stability; (2) the single dispersion and the Pt Thickness Control in the preparation process.Traditional preparation method has following several kinds: (1) colloid method (CN 102500365 A); Promptly at polyelectrolyte (polyvinylpyrrolidone (PVP); Polyvinyl alcohol (PVA) etc.) there is preparation seed colloidal solution down in protective agent, adds another kind of metallic compound then and generates shell in the surface of the seed reduction.Colloid method is simple to operation, but difficult point is how to select suitable protective agent to make subsequent P t particle be coated on the basalis outside to form core/shell structure, rather than independent nucleation; (2) underpotential deposition-displacement method (CN 102500365 A); It is the method that underpotential deposition method and displacement method are combined; At first through undercurrent potential metal is deposited on the basalis, the metal of deposition is replaced by more active metal Pt then, thereby forms core/shell structure.But underpotential deposition-method of replacing process is loaded down with trivial details, and early stage, current potential was sought and difficulty, was not suitable for large-scale production; (3) the removal alloying method is to prepare the PtM metal alloy earlier, then through the surperficial M metal of electrochemical process dissolving, thereby forms the PtMPt catalyst with core-casing structure, and Strasser etc. are with Cu (NO
3)
2Mix in the aqueous solution with commercial Pt/C catalyst, place liquid nitrogen freezing, freeze drying in vacuum tank then, process H in tube furnace
2Heat treatment prepares the PtCu alloy, and the alloy catalyst of preparation passes through the electrochemistry cyclic voltammetry scan at HClO
4The Cu on dissolving surface forms nucleocapsid structure in the solution.Lattice strain when forming the Pt layer is the main cause that catalytic activity improves.(4) chemical reduction method (CN 200910117488) chemical reduction method be with two kinds of metal alloys acid solution or specific gas (like CO, NO, O
2, H
2) middle reaction, thereby make the surface be rich in certain metal.Electrochemical process and chemical reduction method obtained developing rapidly in recent years, adopted this method to be prone to realize nucleocapsid structure, were expected to be used for the mass production of nucleocapsid structure eelctro-catalyst.But to make it introduce other ion post-processed loaded down with trivial details owing to add a large amount of reducing agents and solvents, and flammable explosive gas such as some reduction use hydrogen, and safety coefficient is not high.This method must further be optimized preparation condition, to improve the former activity of oxidation and the stability of catalyst.(5) one stage reduction methods and organic solvent reducing process, a stage reduction method is very similar with colloid method, but the nuclear and the presoma of shell add in the solution simultaneously, in the presence of the structure guiding agent, utilizes the spontaneous formation nucleocapsid structure of difference of different presoma rates of reduction.This method generally uses the higher organic matter of boiling point (like oleic acid, cetylamine and octadecylamine etc.) to make solvent, to be prone to decomposing metal complex (Pd (acac)
2And Pt (acac)
2Deng) be presoma, under inert atmosphere protection, be decomposed to form the nano particle of certain particle size at the higher temperature metal complex, utilize the difference of different presoma decomposition rates to prepare catalyst with core-casing structure.Yamauchi seminar is with K
2PtCl
4, Na
2PdCl
4Being presoma, is stabilizing agent and guiding agent with pluronic P123, is reducing agent with the ascorbic acid, adopts a stage reduction method to prepare the PdPt catalyst with core-casing structure.These two kinds of methods are introduced a large amount of stabilizing agents, guiding agent and reducing agent too, and the unnecessary ion of post-processed is comparatively complicated, and the shell of platinum is thicker, and utilization rate is not high.
Summary of the invention
The objective of the invention is problem, a kind of preparation method of high-activity palladium platinum catalyst with core-casing structure is provided to nucleocapsid catalyst preparation method existence.The present invention at first introduces surface functional groups such as carboxyl, hydroxyl and sulfydryl through chemical oxidation and sulfhydrylation in carbon nano tube surface, through chemical reduction method palladium is loaded on carbon nano tube surface, as " nuclear " of " nuclear/shell " type catalyst; Then, in containing the Pt deionized water solution, utilize the electrical potential difference of Pt and Pd and the weak reducing power of surface functional groups such as carboxyl, hydroxyl and sulfydryl to form the platinum monoatomic layer, as " shell " of " nuclear/shell " type catalyst on the Pd surface.The advantage of this palladium platinum nucleocapsid catalyst is not introduce in the preparation process other stabilizing agent, guiding agent and reducing agent; Advantages such as method is simple; The anchorage effect of sulfydryl can also suppress palladium platinum core-shell nano grows up in migration, the reunion of carrier surface, improves the stability of catalyst.
The objective of the invention is to realize like this: a kind of preparation method of high-activity palladium platinum catalyst with core-casing structure, its concrete grammar step comprises:
(1) bromoization of CNT
In 250 milliliters of round-bottomed flasks, add the commercially available hydroxylating CNT of 0.1 gram, 1.2 gram PBr respectively
3With 160 milliliters of acetone, supersonic oscillations are after 10 minutes, and stirring reaction is 3 hours under room temperature condition; To react the centrifugation earlier of gained mixed liquor then, again with the washing with acetone number all over till do not contain phosphorus tribromide, obtain the CNT of bromoization after drying under the room temperature;
(2) sulfhydrylation of CNT
In 250 milliliters of round-bottomed flasks, add bromo carbon nano tube, 0.8 gram NaHS and 160 milliliters of absolute ethyl alcohols of 0.1 gram (1) step gained respectively, supersonic oscillations are after 20 minutes, and stirring reaction is 4 hours under 20 ℃ of conditions.Then that product is several all over after not containing till the NaHS, not obtaining mercapto carbon nanometer pipe with anhydrous propanone washing;
(3) mercapto carbon nanometer pipe carries the preparation of palladium " nuclear "
The mass ratio of the Tan Na Mi Guan ︰ Ba Yan ︰ Ning lemon of (2) sulfhydrylation of making acid San Na ︰ sodium borohydride is CNT, palladium salt, trisodium citrate and the sodium borohydride that 1 ︰, 0.1～0.5 ︰, 0.33 ~ 1.67 ︰ 2.13 ~ 17.79 takes by weighing sulfhydrylation set by step; With the deionized water solvent with mercapto carbon nanometer pipe, trisodium citrate and palladium salt sonic oscillation 0.5～3 hour; Mechanical agitation was mixed 3～8 hours again; Add sodium borohydride reaction 3～8 hours again; Then product is washed suction filtration and, obtain mercapto carbon nanometer pipe after the grinding and carry palladium " nuclear " 60～100 ℃ of vacuum drying 2～6 hours;
(4) mercapto carbon nanometer pipe carries the preparation of palladium/platinum " nuclear/shell " structure catalyst
Set by step (3) mercapto carbon nanometer pipe of making carry palladium " mass ratio of He ” ︰ platinum salt is that 1 ︰ 0.11～1.67 takes by weighing sulfhydryl anchored palladium " nuclear ", platinum salt; be solvent supersonic vibration 0.5 ~ 4 hour then with the deionized water; regulate pH value to 2～8; fed nitrogen 0.5 ~ 2 hour, product is placed 40 ~ 80 ℃ of reactions 12 ~ 36 hours down, again with product centrifugation, washing; at last under vacuum condition 50～100 ℃ handled 5～24 hours, obtain sulfhydryl anchored palladium/platinum " nuclear/shell " structure catalyst after the grinding.
Wherein said palladium salt is one of them of palladium bichloride, tetrachloro-palladium potassium chlorate.Platinum salt is one of them of chloroplatinic acid, platinum tetrachloride, potassium chloroplatinite.
After the present invention adopts technique scheme, mainly contain following advantage:
(1) utilizes the reducing power of hydroxyl, carboxyl and palladium atom on the mercapto carbon nanometer pipe, the platinum ion reduction on CNT, is formed the individual layer particle, reduced reaction cost and difficulty;
(2) do the nuclear of " nuclear/shell " structure catalyst with palladium, can effectively reduce the platinum carrying capacity, improve the utilization rate of catalyst;
(3) technical scheme of the inventive method can realize a large amount of preparations of catalyst, has broken through fuel cell key technology Study of Catalyst.
It is electrolytical fuel cell that mercapto carbon nanometer pipe palladium/platinum " nuclear/shell " structure catalyst that adopts the present invention to prepare can be applicable to PEM, like the catalyst of hydrogen-oxygen proton exchange membrane fuel cell, DMFC.Fuel cell with the present invention makes is widely used in electric automobile, various spacecrafts, and portable electric appts, like video camera, notebook computer, electronic toy etc.
Description of drawings
Fig. 1 is the transmission electron microscope picture of embodiment 1 prepared mercapto carbon nanometer pipe supported palladium platinum nucleocapsid catalyst.
The cyclic voltammetry curve figure of the mercapto carbon nanometer pipe supported palladium platinum nucleocapsid catalyst that Fig. 2 makes for embodiment 1;
Curve is that the mercapto carbon nanometer pipe supported palladium platinum nucleocapsid catalyst for preparing with embodiment 1 is a working electrode among the figure; Silver/silver chloride electrode is a reference electrode; Platinum loop is to electrode; The saturated 0.1 mol high chloro acid solution of nitrogen is an electrolyte, and sweep speed is 50 millivolts of/second cyclic voltammetry curve figure under the condition.
Fig. 3 is the cyclic voltammetry curve figure contrast of the commercialization Pt/C of Britain Jonhson-Matthey company (platinum mass percent 40%) catalyst (curve 2) and mercapto carbon nanometer pipe supported palladium platinum nucleocapsid catalyst (curve 1);
Curve is that the commercialization Pt/C of the Britain Jonhson-Matthey company catalyst with the contrast experiment is a working electrode among the figure; Silver/silver chloride electrode is a reference electrode; Platinum loop is to electrode; The saturated 0.1 mol high chloro acid solution of nitrogen is an electrolyte, and sweep speed is 50 millivolts of/second cyclic voltammetry curve figure under the condition.
Fig. 4 is the catalytic oxidation-reduction linear scan curve of embodiment 3 gained catalyst and the commercialization Pt/C of Britain Jonhson-Matthey company (platinum mass percent 40%) catalyst;
The specific embodiment
Below in conjunction with the specific embodiment, further specify the present invention.
(1) bromoization of CNT
In 250 milliliters of round-bottomed flasks, add the commercially available hydroxylating CNT of 0.1 gram, 1.2 gram PBr respectively
3With 160 milliliters of acetone, supersonic oscillations are after 10 minutes, and stirring reaction is 3 hours under room temperature condition; To react the centrifugation earlier of gained mixed liquor then, again with the washing with acetone number all over till do not contain phosphorus tribromide, obtain the CNT of bromoization after drying under the room temperature;
(2) sulfhydrylation of CNT
In 250 milliliters of round-bottomed flasks, add bromo carbon nano tube, 0.8 gram NaHS and 160 milliliters of absolute ethyl alcohols of 0.1 gram (1) step gained respectively, supersonic oscillations are after 20 minutes, and stirring reaction is 4 hours under 20 ℃ of conditions.Then that product is several all over after not containing till the NaHS, not obtaining mercapto carbon nanometer pipe with anhydrous propanone washing;
(3) mercapto carbon nanometer pipe carries the preparation of palladium " nuclear "
The mass ratio of the Tan Na Mi Guan ︰ Si chlorine palladium Suan Jia ︰ Ning lemon of (2) sulfhydrylation of making acid San Na ︰ sodium borohydride is CNT, tetrachloro-palladium potassium chlorate, trisodium citrate and the sodium borohydride that 1 ︰, 0.3 ︰, 1 ︰ 17.79 takes by weighing sulfhydrylation set by step; With the deionized water solvent with mercapto carbon nanometer pipe, trisodium citrate and tetrachloro-palladium potassium chlorate sonic oscillation 2 hours; Mechanical agitation was mixed 3 hours again; Add sodium borohydride reaction 8 hours again; Then product is washed suction filtration and, obtain mercapto carbon nanometer pipe after the grinding and carry palladium " nuclear " 60 ℃ of vacuum drying 2 hours;
(4) mercapto carbon nanometer pipe carries the preparation of palladium/platinum " nuclear/shell " structure catalyst
Set by step (3) mercapto carbon nanometer pipe of making carry palladium " mass ratio of He ” ︰ potassium chloroplatinite is that 1 ︰ 0.8 takes by weighing sulfhydryl anchored palladium " nuclear ", potassium chloroplatinite; be solvent supersonic vibration 2 hours then with the deionized water, regulate pH value to 8, fed nitrogen 2 hours; product is placed 60 ℃ of reactions 24 hours down; again with product centrifugation, washing, at last under vacuum condition 70 ℃ handled 12 hours, obtain sulfhydryl anchored palladium/platinum " nuclear/shell " structure catalyst after the grinding;
(5) the hydrogen reduction active testing of mercapto carbon nanometer pipe supported palladium/platinum " nuclear/shell " structure catalyst
Taking by weighing 2 milligram of (4) step prepared sulfhydryl anchored palladium/platinum " nuclear/shell " structure catalyst joins after sonic oscillation was uniformly dispersed in 20 minutes in 0.2 milliliter of absolute ethyl alcohol; Microsyringe is drawn 10 microlitres and is dripped on the vitreous carbon rotating disk electrode (r.d.e); After the ethanol saturated vapor is depressed drying; Draw 0.5 microlitre quality percentage composition again and be 0.1% Nafion ethanolic solution and drip on Catalytic Layer, 80 ℃ kept 2 hours down.As working electrode, respectively as auxiliary electrode and reference electrode, cyclic voltammetry scan is estimated the stability of gained catalyst fast in the perchloric acid solution of 0.1 saturated mol of nitrogen with platinum loop electrode and palladium/palladium salt electrode.Sweep speed is 50 millivolts/second, and sweep limits is-0.2～1 volt (with respect to silver/silver chloride electrode), the curve in the corresponding diagram 1.
Step (1) (2) is with step (1) (2) among the embodiment 1;
(3) mercapto carbon nanometer pipe carries the preparation of palladium " nuclear "
The mass ratio of the Tan Na Mi Guan ︰ Lvization Ba ︰ Ning lemon of (2) sulfhydrylation of making acid San Na ︰ sodium borohydride is CNT, palladium bichloride, trisodium citrate and the sodium borohydride that 1 ︰, 0.1 ︰, 1.67 ︰ 10 take by weighing sulfhydrylation set by step; With the deionized water solvent with mercapto carbon nanometer pipe, trisodium citrate and palladium bichloride sonic oscillation 3 hours; Mechanical agitation was mixed 6 hours again; Add sodium borohydride reaction 5 hours again; Then product is washed suction filtration and, obtain mercapto carbon nanometer pipe after the grinding and carry palladium " nuclear " 80 ℃ of vacuum drying 4 hours;
(4) mercapto carbon nanometer pipe carries the preparation of palladium/platinum " nuclear/shell " structure catalyst
Set by step (3) mercapto carbon nanometer pipe of making carry palladium " mass ratio of He ” ︰ chloroplatinic acid is that 1 ︰ 0.11 takes by weighing sulfhydryl anchored palladium " nuclear ", chloroplatinic acid; be solvent supersonic vibration 0.5 hour then with the deionized water, regulate pH value to 5, fed nitrogen 0.5 hour; product is placed 80 ℃ of reactions 36 hours down; again with product centrifugation, washing, at last under vacuum condition 50 ℃ handled 24 hours, obtain sulfhydryl anchored palladium/platinum " nuclear/shell " structure catalyst after the grinding;
(5) the electrochemistry situation of mercapto carbon nanometer pipe supported palladium/platinum " nuclear/shell " structure catalyst
Taking by weighing 2 milligram of (4) step prepared mercapto carbon nanometer pipe supported palladium/platinum " nuclear/shell " structure catalyst joins after sonic oscillation was uniformly dispersed in 20 minutes in the mixed liquor of being made up of 0.2 milliliter of ultra-pure water and 0.2 milliliter of absolute ethyl alcohol; Microsyringe is drawn 10 microlitres and is dripped on the vitreous carbon rotating disk electrode (r.d.e); After the ethanol saturated vapor is depressed drying; Draw 0.5 microlitre quality percentage composition again and be 0.1% Nafion ethanolic solution and drip on Catalytic Layer, 80 ℃ kept 2 hours down.As working electrode, respectively as auxiliary electrode and reference electrode, cyclic voltammetry scan is estimated the stability of gained catalyst fast in the perchloric acid solution of 0.1 saturated mol of nitrogen with platinum loop electrode and palladium/palladium salt electrode.Sweep speed is 50 millivolts/second, and sweep limits is-0.2～1 volt (with respect to silver/silver chloride electrode), scans 50 circles altogether.The electrochemical surface of estimating platinum with the electric weight of absorption hydrogen in the hydrogen adsorption desorption district in the cyclic voltammetry curve is long-pending, the curve 1 in the corresponding diagram 3.
Step (1) (2) is with step (1) (2) among the embodiment 1;
(3) mercapto carbon nanometer pipe carries the preparation of palladium " nuclear "
The mass ratio of the Tan Na Mi Guan ︰ Si chlorine palladium Suan Jia ︰ Ning lemon of (2) sulfhydrylation of making acid San Na ︰ sodium borohydride is CNT, tetrachloro-palladium potassium chlorate, trisodium citrate and the sodium borohydride that 1 ︰, 0.5 ︰, 0.33 ︰ 2.13 takes by weighing sulfhydrylation set by step; With the deionized water solvent with mercapto carbon nanometer pipe, trisodium citrate and tetrachloro-palladium potassium chlorate sonic oscillation 0.5 hour; Mechanical agitation was mixed 8 hours again; Add sodium borohydride reaction 3 hours again; Then product is washed suction filtration and, obtain mercapto carbon nanometer pipe after the grinding and carry palladium " nuclear " 100 ℃ of vacuum drying 6 hours;
(4) mercapto carbon nanometer pipe carries the preparation of palladium/platinum " nuclear/shell " structure catalyst
Set by step (3) mercapto carbon nanometer pipe of making carry palladium " mass ratio of He ” ︰ platinum tetrachloride is that 1 ︰ 1.67 takes by weighing sulfhydryl anchored palladium " nuclear ", platinum tetrachloride; be solvent supersonic vibration 4 hours then with the deionized water, regulate pH value to 2, fed nitrogen 1 hour; product is placed 40 ℃ of reactions 12 hours down; again with product centrifugation, washing, at last under vacuum condition 100 ℃ handled 5 hours, obtain sulfhydryl anchored palladium/platinum " nuclear/shell " structure catalyst after the grinding;
(5) the electrochemistry situation of mercapto carbon nanometer pipe supported palladium/platinum " nuclear/shell " structure catalyst
Taking by weighing 2 milligram of (4) step prepared mercapto carbon nanometer pipe supported palladium/platinum " nuclear/shell " structure catalyst joins after sonic oscillation was uniformly dispersed in 20 minutes in the mixed liquor of being made up of 0.2 milliliter of ultra-pure water and 0.2 milliliter of absolute ethyl alcohol; Microsyringe is drawn 10 microlitres and is dripped on the vitreous carbon rotating disk electrode (r.d.e); After the ethanol saturated vapor is depressed drying; Draw 0.5 microlitre quality percentage composition again and be 0.1% Nafion ethanolic solution and drip on Catalytic Layer, 80 ℃ kept 2 hours down.As working electrode, respectively as auxiliary electrode and reference electrode, the hydrogen reduction of gained catalyst is estimated fast in the perchloric acid solution neutral line scanning of 0.1 saturated mol of nitrogen with platinum loop electrode and palladium/palladium salt electrode.Sweep speed is 10 millivolts/second, and sweep limits is 0～1 volt (with respect to silver/silver chloride electrode), the curve 1 in the corresponding diagram 4.
The contrast experiment
The cyclic voltammetric test of the commercialization Pt/C of Britain Jonhson-Matthey company (platinum mass percent 40%) catalyst is with step (5) among the embodiment 2, the curve 2 in the corresponding diagram 3.
The test of the hydrogen reduction catalytic performance of the commercialization Pt/C of Britain Jonhson-Matthey company (platinum mass percent 40%) catalyst is with step (5) among the embodiment 3, the curve 2 in the corresponding diagram 4.
Result of the test of the present invention:
As can beappreciated from fig. 4; Bend over the desk after the scanning through 50 circle circulations; Adopting hydrogen suctions/desorption district area that the prepared mercapto carbon nanometer pipe of the present invention carries palladium platinum catalyst with core-casing structure is 1.5 times of hydrogen suction/desorption district area of the commercialization Pt/C of Britain Jonhson-Matthey company catalyst, and this explains that mercapto carbon nanometer pipe carries palladium platinum catalyst with core-casing structure and exceeds much than the electrochemical site of the commercialization Pt/C of Jonhson-Matthey company catalyst.
As can be seen from Figure 4; Hydrogen reduction take-off potential and half wave potential that the prepared mercapto carbon nanometer pipe of the present invention carries palladium platinum catalyst with core-casing structure have had than Jonhson-Matthey company commercialization Pt/C catalyst and have significantly improved, and it is active that this shows that the prepared mercapto carbon nanometer pipe of the present invention carries the hydrogen reduction higher than having of the commercialization Pt/C of Jonhson-Matthey company catalyst of palladium platinum catalyst with core-casing structure.
Claims (5)
1. the preparation method of a high-activity palladium platinum catalyst with core-casing structure, its concrete grammar step comprises
(1) bromoization of CNT
In 250 milliliters of round-bottomed flasks, add the commercially available hydroxylating CNT of 0.1 gram, 1.2 gram PBr respectively
3With 160 milliliters of acetone, supersonic oscillations are after 10 minutes, and stirring reaction is 3 hours under room temperature condition; To react the centrifugation earlier of gained mixed liquor then, again with the washing with acetone number all over till do not contain phosphorus tribromide, obtain the CNT of bromoization after drying under the room temperature;
(2) sulfhydrylation of CNT
In 250 milliliters of round-bottomed flasks, add bromo carbon nano tube, 0.8 gram NaHS and 160 milliliters of absolute ethyl alcohols of 0.1 gram (1) step gained respectively, supersonic oscillations are after 20 minutes, and stirring reaction is 4 hours under 20 ℃ of conditions; Then that product is several all over after not containing till the NaHS, not obtaining mercapto carbon nanometer pipe with anhydrous propanone washing;
It is characterized in that:
(3) mercapto carbon nanometer pipe carries the preparation of palladium " nuclear "
The mass ratio of the Tan Na Mi Guan ︰ Ba Yan ︰ Ning lemon of (2) sulfhydrylation of making acid San Na ︰ sodium borohydride is CNT, palladium salt, trisodium citrate and the sodium borohydride that 1 ︰, 0.1～0.5 ︰, 0.33 ~ 1.67 ︰ 2.13 ~ 17.79 takes by weighing sulfhydrylation set by step; With the deionized water solvent with mercapto carbon nanometer pipe, trisodium citrate and palladium salt sonic oscillation 0.5～3 hour; Mechanical agitation was mixed 3～8 hours again; Add sodium borohydride reaction 3～8 hours again; Then product is washed suction filtration and, obtain mercapto carbon nanometer pipe after the grinding and carry palladium " nuclear " 60～100 ℃ of vacuum drying 2～6 hours;
(4) mercapto carbon nanometer pipe carries the preparation of palladium/platinum " nuclear/shell " structure catalyst
Set by step (3) mercapto carbon nanometer pipe of making carry palladium " mass ratio of He ” ︰ platinum salt is that 1 ︰ 0.11～1.67 takes by weighing sulfhydryl anchored palladium " nuclear ", platinum salt; be solvent supersonic vibration 0.5 ~ 4 hour then with the deionized water; regulate pH value to 2～8; fed nitrogen 0.5 ~ 2 hour, product is placed 40 ~ 80 ℃ of reactions 12 ~ 36 hours down, again with product centrifugation, washing; at last under vacuum condition 50～100 ℃ handled 5～24 hours, obtain sulfhydryl anchored palladium/platinum " nuclear/shell " structure catalyst after the grinding.
2. according to the preparation method of the described a kind of high-activity palladium platinum catalyst with core-casing structure of claim 1, it is characterized in that one of them that described palladium salt is palladium bichloride, tetrachloro-palladium potassium chlorate; Platinum salt is one of them of chloroplatinic acid, platinum tetrachloride, potassium chloroplatinite.
3. according to the preparation method of the described a kind of high-activity palladium platinum catalyst with core-casing structure of claim 1, it is characterized in that concrete preparation method's step (3)～(4):
(3) mercapto carbon nanometer pipe carries the preparation of palladium " nuclear "
The mass ratio of the Tan Na Mi Guan ︰ Si chlorine palladium Suan Jia ︰ Ning lemon of (2) sulfhydrylation of making acid San Na ︰ sodium borohydride is CNT, tetrachloro-palladium potassium chlorate, trisodium citrate and the sodium borohydride that 1 ︰, 0.3 ︰, 1 ︰ 17.79 takes by weighing sulfhydrylation set by step; With the deionized water solvent with mercapto carbon nanometer pipe, trisodium citrate and tetrachloro-palladium potassium chlorate sonic oscillation 2 hours; Mechanical agitation was mixed 3 hours again; Add sodium borohydride reaction 8 hours again; Then product is washed suction filtration and, obtain mercapto carbon nanometer pipe after the grinding and carry palladium " nuclear " 60 ℃ of vacuum drying 2 hours;
(4) mercapto carbon nanometer pipe carries the preparation of palladium/platinum " nuclear/shell " structure catalyst
Set by step (3) mercapto carbon nanometer pipe of making carry palladium " mass ratio of He ” ︰ potassium chloroplatinite is that 1 ︰ 0.8 takes by weighing sulfhydryl anchored palladium " nuclear ", potassium chloroplatinite; be solvent supersonic vibration 2 hours then with the deionized water, regulate pH value to 8, fed nitrogen 2 hours; product is placed 60 ℃ of reactions 24 hours down; again with product centrifugation, washing, at last under vacuum condition 70 ℃ handled 12 hours, obtain sulfhydryl anchored palladium/platinum " nuclear/shell " structure catalyst after the grinding.
4. according to the preparation method of the described a kind of high-activity palladium platinum catalyst with core-casing structure of claim 1, it is characterized in that concrete preparation method's step (3)～(4):
(3) mercapto carbon nanometer pipe carries the preparation of palladium " nuclear "
The mass ratio of the Tan Na Mi Guan ︰ Lvization Ba ︰ Ning lemon of (2) sulfhydrylation of making acid San Na ︰ sodium borohydride is CNT, palladium bichloride, trisodium citrate and the sodium borohydride that 1 ︰, 0.1 ︰, 1.67 ︰ 10 take by weighing sulfhydrylation set by step; With the deionized water solvent with mercapto carbon nanometer pipe, trisodium citrate and palladium bichloride sonic oscillation 3 hours; Mechanical agitation was mixed 6 hours again; Add sodium borohydride reaction 5 hours again; Then product is washed suction filtration and, obtain mercapto carbon nanometer pipe after the grinding and carry palladium " nuclear " 80 ℃ of vacuum drying 4 hours;
(4) mercapto carbon nanometer pipe carries the preparation of palladium/platinum " nuclear/shell " structure catalyst
Set by step (3) mercapto carbon nanometer pipe of making carry palladium " mass ratio of He ” ︰ chloroplatinic acid is that 1 ︰ 0.11 takes by weighing sulfhydryl anchored palladium " nuclear ", chloroplatinic acid; be solvent supersonic vibration 0.5 hour then with the deionized water, regulate pH value to 5, fed nitrogen 0.5 hour; product is placed 80 ℃ of reactions 36 hours down; again with product centrifugation, washing, at last under vacuum condition 50 ℃ handled 24 hours, obtain sulfhydryl anchored palladium/platinum " nuclear/shell " structure catalyst after the grinding.
5. according to the preparation method of the described a kind of high-activity palladium platinum catalyst with core-casing structure of claim 1, it is characterized in that concrete preparation method's step (3)～(4):
(3) mercapto carbon nanometer pipe carries the preparation of palladium " nuclear "
The mass ratio of the Tan Na Mi Guan ︰ Si chlorine palladium Suan Jia ︰ Ning lemon of (2) sulfhydrylation of making acid San Na ︰ sodium borohydride is CNT, tetrachloro-palladium potassium chlorate, trisodium citrate and the sodium borohydride that 1 ︰, 0.5 ︰, 0.33 ︰ 2.13 takes by weighing sulfhydrylation set by step; With the deionized water solvent with mercapto carbon nanometer pipe, trisodium citrate and tetrachloro-palladium potassium chlorate sonic oscillation 0.5 hour; Mechanical agitation was mixed 8 hours again; Add sodium borohydride reaction 3 hours again; Then product is washed suction filtration and, obtain mercapto carbon nanometer pipe after the grinding and carry palladium " nuclear " 100 ℃ of vacuum drying 6 hours;
(4) mercapto carbon nanometer pipe carries the preparation of palladium/platinum " nuclear/shell " structure catalyst
Set by step (3) mercapto carbon nanometer pipe of making carry palladium " mass ratio of He ” ︰ platinum tetrachloride is that 1 ︰ 1.67 takes by weighing sulfhydryl anchored palladium " nuclear ", platinum tetrachloride; be solvent supersonic vibration 4 hours then with the deionized water, regulate pH value to 2, fed nitrogen 1 hour; product is placed 40 ℃ of reactions 12 hours down; again with product centrifugation, washing, at last under vacuum condition 100 ℃ handled 5 hours, obtain sulfhydryl anchored palladium/platinum " nuclear/shell " structure catalyst after the grinding.
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